CN101703866A - Smoke alkali-free adsorption type biological desulphurization technology - Google Patents
Smoke alkali-free adsorption type biological desulphurization technology Download PDFInfo
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- CN101703866A CN101703866A CN200910075781A CN200910075781A CN101703866A CN 101703866 A CN101703866 A CN 101703866A CN 200910075781 A CN200910075781 A CN 200910075781A CN 200910075781 A CN200910075781 A CN 200910075781A CN 101703866 A CN101703866 A CN 101703866A
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- water
- smoke
- desulfurization wastewater
- desulfurization
- sulfur
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Abstract
The invention discloses a smoke alkali-free adsorption type biological desulphurization technology which mainly comprises the following steps: alkali does not need to be added into absorption liquid in an adsorption tower; desulphurization of desulfurated waste water is completed by an technology of adopting an oblique plate sedimentation tank, an adjusting tank, a carbon adding source, an up-flow sludge bed reactor, a middle sedimentation tank, a contact oxidation tank and a secondary sedimentation tank; the adjusting tank is divided into 10 small adjusting tanks and adopts a plug flow structure, so that the temperature of the desulfurated waste water is gradually decreased; and the water which flows out of the secondary sedimentation tank is filtered by a falling curtain type ultrafiltration membrane to concentrate simple substance sulphur-containing water. The technology reduces the operation cost of the desulphurization of the smoke, eliminates the secondary pollution of secondary products caused by the desulphurization, and coverts sulfur dioxide and sulfur trioxide in the smoke into the simple substance sulphur under the function of microorganism.
Description
Technical field:
The present invention relates to a kind of flue gas desulfurization technique, is a kind of technology that adopts the alkali-free adsorption type biological desulphurization method to administer waste gas and water pollution control, and it is particularly related to flue gas desulfurization process of fire coal and sulfur-bearing hydrochlorate waste water treatment process.
Background technology:
Present right coal flue gas desulfurization technique mainly contains three classes: wet desulphurization technology, half dry type desulfur technology and dry type desulfurizing technology.
1, wet type desulfurizing technology:
It is several that the wet type desulfurizing technology mainly contains lime/lime stone-gypsum method, MgO method, ammonium sulfite, two alkaline process etc., its desulfuration efficiency height, wide accommodation, low, the technology maturation of calcium sulfur ratio.
But the wet process of FGD technology has shortcomings such as operating cost height and specification requirement height.There is the problem of recycling difficulty in byproduct.
2, half dry type desulfur technology:
The main rotary spraying and drying method of half dry type desulfur technology, pressure spray thing seasoning etc., this technology does not have desulfurization wastewater to produce, do not need desulfurization wastewater treatment facility and facility, invest relatively low, generally be equal scale the gypsum method flue gas desulfurization system about 70%.Desulfuration efficiency medium 80 ~ 90%.
But exist high humidity, dew point after the flue gas spray-drying wayward, follow-up cleaner operation ratio is low, and maintenance capacity is big; And exist that amount of lime is big, the absorbent utilization rate low and desulfurization after the difficult problem utilized again of byproduct.
3, half dry type desulfur technology:
The dry type desulfurizing technology mainly contains electronic beam method, charged dry-type jetting doctor treatment, impulse electric corona method etc., and the no liquid phase of this technology reaction gets involved, and product also is a dry powder, does not have problems such as burn into dewfall, does not have the equipment corrosion problem.Do not need waste water disposal facility, desulfurization simultaneously is out of stock.Byproduct is good composite fertilizer.Desulfuration efficiency is higher than 90%.
But this technical equipment costliness, system's operation, maintenance technology require high.The key equipment parts do not pass a test, and operation troubles is many.
Summary of the invention:
The object of the invention is to overcome the deficiencies in the prior art, a kind of smoke alkali-free adsorption type biological desulphurization technology is provided, the flue gas desulfurization operating cost is reduced, and sulfur in smoke and sulfur trioxide be converted into elemental sulfur by action of microorganisms, make the existing environmental benefit of flue gas desulfurization, have an economic benefit again.Eliminate the secondary pollution of desulfuration byproduct simultaneously.
Purpose of the present invention can realize by following technical scheme:
A kind of smoke alkali-free adsorption type biological desulphurization technology, its processing step such as following:
1, flue gas absorbing unit:
Adsorption tower adopts the spray column structure, and coal-fired flue-gas enters in the adsorption tower by pipeline, is forced into 3Kg/cm with process
2And fully contact through the absorption liquid water smoke of clog-free shower nozzle ejection, the PH of absorption liquid remains between the 7-8, and sulfur in smoke and sulfur trioxide are absorbed by liquid absorption and are transferred in the absorption liquid, thereby finish the sweetening process of flue gas.The absorption liquid that absorbs sulfur dioxide and sulfur trioxide is discharged adsorption tower formation desulfurization wastewater.
2, desulfurization wastewater biological desulphurization unit:
(1) Anaerobic Treatment unit:
Desulfurization wastewater at first enters inclined-plate clarifying basin, the surface loading of inclined-plate clarifying basin: 0.5m
3/ (m
2.h), in inclined-plate clarifying basin, realize separating of desulfurization wastewater and flue dust; Then, the desulfurization wastewater of separating enters regulating reservoir, and it is 5 days desulfurization wastewater that the regulating reservoir volume can hold, and regulating reservoir divides 10 minor adjustment ponds, adopts the pulling flow type structure, and the temperature of desulfurization wastewater is reduced gradually.Each minor adjustment pond is equipped with a sewage pump.And in desulfurization wastewater, adding carbon source simultaneously, the carbon source that adds can be starch, glucose, ethanol, methyl alcohol, acetate, molasses, house refuse acid fermentation product etc.Make the COD/ (SO that adds the desulfurization wastewater after the carbon source
3 2-+ SO
4 2-) 〉=2.0.
Select the desulfurization wastewater temperature to enter in the up flow anaerobic sludge blanket reactor in the lifting of the waste water of 35 ℃-40 ℃ regulating reservoir by pump, the environment of 30 ℃-35 ℃ of necessary holding temperatures, basicity 1500-2500mg/L, PH=7.5-8.0 in the up flow anaerobic sludge blanket reactor, the COD volumetric loading of up flow anaerobic sludge blanket reactor is 6-8KgCOD/ (m
3.d), the load of sulfate ion and sulfite ion is 3-4KgCOD/ (m
3.d), the desulfurization wastewater that enters up flow anaerobic sludge blanket reactor utilizes sulfate reducing bacteria that sulphite in the desulfurization wastewater and sulfate are reduced into sulfide and hydrogen sulfide under the condition of additional carbon; Concrete reaction equation (is carbon source with methyl alcohol):
HSO
3 -+CH
3OH——HS
-+CO
2↑+2H
2O
3SO
4 2-+4CH
3OH——3HS
-+3HCO
3 -+CO
2↑+5H
2O
If basicity is low, PH is lower than 7.0, and following reaction then takes place:
H
++HS
-——H
2S
Produce hydrogen sulfide, a hydrogen sulfide part is overflowed, and a part is soluble in water.
From the effect in the waste water process intermediate sedimentation pond that up flow anaerobic sludge blanket reactor flows out, the anaerobic sludge that waste water is carried is separated with waste water.
(2) Aerobic Process for Treatment unit:
The waste water that flows out from middle sedimentation basin enters the contact-oxidation pool, temperature 22-30 ℃, PH=7.5-8.0 in the contact-oxidation pool, sulfide load: 9-12Kg/ (m
3.d), H
2S load: 4.0-6.0Kg/ (m
3.d).Make good use of the oxygen animalcule colorless sulfur bacteria sulfide and hydrogen sulfide are oxidized to elemental sulfur.
Reaction equation:
Main reaction: 2HS
-+ O2---2S ↓+2OH
-
Pay reaction: 2H
2S+O
2---2S
0↓+2H
2O
H
2S+2O
2——H
2SO
4
Back reaction: 2S
0+ O
2+ 2H
2O---2H
2SO
4
When the sulfide load is low, pay reaction H
2S+2O
2-H
2SO
4Take place, make the SO of water outlet
4 2-Concentration raises, and the PH of water outlet reduces.Arrive to a certain degree when the sulfide load is low, then back reaction 2S
0+ O
2+ 2H
2O-2H
2SO
4Take place, also make the SO of water outlet
4 2-Concentration raises, and the PH of water outlet reduces.Make when sulfide and load when high, pay reaction 2H
2S+O
2-2S
0+ 2H
2O takes place, SO
4 2-The then less rising of concentration, even also descend, the PH of water outlet raises.
Keep the sulfide high load capacity, contact-oxidation pool can keep good operational effect, makes sulfide and hydrogen sulfide the highest to the conversion ratio of elemental sulfur; And be difficult for taking place SO in the water outlet
4 2-The phenomenon that concentration raises, service condition are easy to control, and operational effect is comparatively stable.Desulfuration efficiency is stabilized in more than 97%.
The waste water that flows out from contact-oxidation pool realizes second pond and the separating of activated sludge, and enters the ultrafiltration concentration basin from the waste water of second pond outflow, by the curtain falling type milipore filter water extracted out, and the water of extraction enters circulating water pool to be continued back to use in the adsorption tower.
3, simple substance sulfur recovery unit:
0.14,0.18,0.23,0.27m/h concentrate in the ultrafiltration concentration basin enters the slow filter and carries out Separation of Solid and Liquid, the slow filter filtering velocity under the lifting of pump:.After finishing filter cycle, the layer of sand of holding back surface, the slow filter 5 ~ 6cm of simple substance sulphur granule is scraped, sand and elemental sulfur mixture are extracted, distill, can obtain the higher elemental sulfur of purity with carbon disulfide.Extractant carbon disulfide recycles.
Process characteristic of the present invention is as follows:
1, the absorption liquid in the adsorption tower does not need to add alkali: add NaOH with common clear water during startup and squeeze in the adsorption tower as absorption liquid, fully contact with flue gas, absorb sulfur in smoke and sulfur trioxide; The basicity of the circulating absorption solution that increases in the dependence sequencing batch active sludge running in service is afterwards kept the stable of whole absorption liquid circulatory system PH.
2, utilize up flow anaerobic sludge blanket reactor and two microbiological treatment cell processing of contact-oxidation pool desulfurization wastewater: utilize the sulfate reducing bacteria in the up flow anaerobic sludge blanket reactor that sulphite in the desulfurization wastewater and sulfate are reduced into sulfide and hydrogen sulfide under the condition of additional carbon; Utilize the colorless sulfur bacteria in the contact-oxidation pool that sulfide and hydrogen sulfide are oxidized to elemental sulfur, through second pond water is separated with activated sludge then.Desulfurization wastewater after the processing returns adsorption tower and recycles.
3, reclaim elemental sulfur: utilize the curtain falling type milipore filter to concentrate the second pond water outlet, concentrate obtains elemental sulfur through slow filter → extraction with carbon disulfide → operations such as distillation.Extractant recycles.
Advantage of the present invention is: adopt smoke alkali-free adsorption type biological desulphurization technology that the flue gas desulfurization operating cost is reduced, eliminate the secondary pollution of desulfuration byproduct simultaneously.And sulfur in smoke and sulfur trioxide be converted into elemental sulfur by action of microorganisms.
Description of drawings:
Accompanying drawing is a process chart of the present invention
The specific embodiment:
A kind of smoke alkali-free adsorption type biological desulphurization technology, its processing step such as following:
1, flue gas adsorption process:
Absorption liquid is stored in the circulating water pool, by entering in the adsorption tower after the pump pressurization; Flue gas fully stirs, contacts with the absorption liquid of PH=7.0-8.0 in piping enters adsorption tower, and sulfur in smoke and sulfur trioxide are absorbed by liquid absorption, and the flue gas after the desulfurization passes through the chimney qualified discharge under the power traction of air-introduced machine.
The absorption liquid that absorbs sulfur dioxide and sulfur trioxide is discharged adsorption tower and is become desulfurization wastewater.
2, desulfurization wastewater biological desulphurization flow process:
Desulfurization wastewater at first enters inclined-plate clarifying basin, realizes separating of desulfurization wastewater and flue dust in inclined-plate clarifying basin; The desulfurization wastewater of then separating enters regulating reservoir, and adds carbon source simultaneously in desulfurization wastewater.
The waste water of regulating reservoir enters in the up flow anaerobic sludge blanket reactor by the lifting of pump, and the desulfurization wastewater that enters up flow anaerobic sludge blanket reactor utilizes sulfate reducing bacteria that sulphite in the desulfurization wastewater and sulfate are reduced into sulfide and hydrogen sulfide under the condition of additional carbon.
From the effect in the waste water process intermediate sedimentation pond that up flow anaerobic sludge blanket reactor flows out, the anaerobic sludge that waste water is carried is separated with waste water.
The waste water that flows out from middle sedimentation basin enters the contact-oxidation pool, makes good use of the oxygen animalcule colorless sulfur bacteria in contact-oxidation pool sulfide and hydrogen sulfide are oxidized to elemental sulfur.The waste water that flows out from contact-oxidation pool is realized second pond and the separating of activated sludge, the waste water that flows out from second pond enters the ultrafiltration concentration basin, by the curtain falling type ultrafiltration membrance filter, under the traction of self priming pump, water to be extracted out, the water of extraction enters circulating water pool to be continued back to use in the adsorption tower.
Concentrate in the ultrafiltration concentration basin enters the slow filter and carries out Separation of Solid and Liquid under the lifting of pump, the water of separating returns circulating water pool to be continued back to use in the adsorption tower.
The flue dust of sloping plate deposition deposition is discharged by mud outflow machine, and outward transport is handled.
Enter sludge-tank from the residual active sludge of middle sedimentation basin and second pond discharge, enter under the lifting of sludge pump in the mud centrifugal separator and dewater, the mud cake outward transport after the dehydration is handled.The water of deviating from returns regulating reservoir and continues to accept processing.
3, elemental sulfur recovery process:
Finish the filter cycle of slow filter, the layer of sand of holding back surface, the slow filter 5 ~ 6cm of simple substance sulphur granule is scraped, putting into abstraction pool extracts, extract adopts carbon disulfide, extract behind the extraction elemental sulfur is promoted in the destilling tower by pump and distills, the steam that distills obtains carbon disulfide liquid by condenser condenses, and extractant carbon disulfide recycles.The destilling tower bottom can obtain the higher elemental sulfur of purity.
Filter sand excessively in the abstraction pool can continue back to use in the slow filter.
Claims (4)
1. smoke alkali-free adsorption type biological desulphurization technology is characterized in that: its processing step such as following:
(1) need carry out the flue gas that desulfurization handles and at first enter adsorption tower by pipeline, the adsorption tower domestic demand carry out flue gas that desulfurization handles with through being forced into 3Kg/cm
2And the absorption liquid water smoke that sprays through clog-free shower nozzle fully contacts, the PH of absorption liquid remains between the 7-8, the sulfur in smoke and the sulfur trioxide that need carry out the desulfurization processing are absorbed by liquid absorption and are transferred in the absorption liquid, thereby finish the sweetening process of flue gas;
(2) absorption liquid that absorbs sulfur dioxide and sulfur trioxide is discharged adsorption tower formation desulfurization wastewater, and desulfurization wastewater at first enters inclined-plate clarifying basin, and the surface loading of inclined-plate clarifying basin is: 0.5m
3/ (m
2.h), then flow into regulating reservoir, the total measurement (volume) of regulating reservoir is for can hold 5 days desulfurization wastewater, described regulating reservoir divides 10 minor adjustment ponds, the pulling flow type structures are adopted in 10 minor adjustment ponds, reduce gradually through the temperature of 10 minor adjustment pond desulfurization wastewaters, and each minor adjustment pond is equipped with a sewage pump.In desulfurization wastewater, add carbon source, make the COD/ (SO that adds the desulfurization wastewater after the carbon source
3 2-+ SO
4 2-) 〉=2.0, the carbon source that is added are starch, or the carbon source that is added is the acid fermentation product of glucose or ethanol, methyl alcohol, acetate, molasses, house refuse;
(3) select the desulfurization wastewater temperature to enter in the up flow anaerobic sludge blanket reactor in the lifting of the waste water of 35 ℃-40 ℃ regulating reservoir by pump, the environment of 30 ℃-35 ℃ of necessary holding temperatures, basicity 1500-2500mg/L, PH=7.5-8.0 in the up flow anaerobic sludge blanket reactor, the COD volumetric loading of up flow anaerobic sludge blanket reactor is 6-8KgCOD/ (m
3.d), the load of sulfate ion and sulfite ion is 3-4KgCOD/ (m
3.d), the desulfurization wastewater that enters up flow anaerobic sludge blanket reactor utilizes sulfate reducing bacteria that sulphite in the desulfurization wastewater and sulfate are reduced into sulfide and hydrogen sulfide under the condition of additional carbon; The waste water that flows out from up flow anaerobic sludge blanket reactor flows into the intermediate sedimentation pond, and the waste water that flows out from middle sedimentation basin enters the contact-oxidation pool, 22 ℃-30 ℃ of temperature, PH=7.5-8.0 in the contact-oxidation pool, sulfide load: 9-12Kg/ (m
3.d), H
2S load: 4.0-6.0Kg/ (m
3.d); Make good use of the oxygen animalcule colorless sulfur bacteria sulfide and hydrogen sulfide are oxidized to elemental sulfur; The waste water that flows out from contact-oxidation pool realizes second pond and the separating of activated sludge, and enters the ultrafiltration concentration basin from the waste water of second pond outflow, by the curtain falling type milipore filter water extracted out, and the water of extraction enters circulating water pool to be continued back to use in the adsorption tower;
(4) concentrate in the ultrafiltration concentration basin enters the slow filter and carries out Separation of Solid and Liquid, slow filter filtering velocity: 0.14-0.27m/h under the lifting of pump; The water that filters out returns circulating water pool to be continued to use; After finishing filter cycle, the layer of sand of holding back surface, the slow filter 5-6cm of simple substance sulphur granule is scraped, with carbon disulfide sand and elemental sulfur mixture are extracted, distill, to obtain the higher elemental sulfur of purity, extractant carbon disulfide recycles.
2. smoke alkali-free adsorption type biological desulphurization technology according to claim 1, it is characterized in that: add NaOH as absorption liquid with common clear water during startup, the basicity of the circulating absorption solution that increases in the dependence sequencing batch active sludge running in service is afterwards kept the stable of whole absorption liquid circulatory system PH.
3. smoke alkali-free adsorption type biological desulphurization technology according to claim 1 is characterized in that: employing sloping plate deposition → regulating reservoir → add carbon source → up-flow sludge bed reactor → intermediate sedimentation pond → contact-oxidation pool → second pond technology to finish the desulfurization of desulfurization wastewater.
4. smoke alkali-free adsorption type biological desulphurization technology according to claim 1 is characterized in that: adopt the water outlet of curtain falling type ultrafiltration membrance filter second pond, follow-up elemental sulfur reclaimer and facility are reduced significantly.
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Cited By (9)
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| CN102180549A (en) * | 2011-03-29 | 2011-09-14 | 重庆大学 | Method and system for zero emission treatment of desulfured waste water |
| CN102451607A (en) * | 2010-10-21 | 2012-05-16 | 李红玉 | Internal and external dual-circulation reaction method and device for absorbing hydrogen sulfide |
| CN103145244A (en) * | 2013-03-01 | 2013-06-12 | 中国石油化工股份有限公司 | Synergistic biological treatment method for washing waste water and amine salt waste liquor produced by capturing CO2 in smoke of coal-fired power plant |
| CN104801166A (en) * | 2015-04-22 | 2015-07-29 | 华南师范大学 | Method and device for cooperative flue gas desulfurization and sewage organic matter degradation and denitrification |
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| CN110550608A (en) * | 2019-09-18 | 2019-12-10 | 中国石油化工股份有限公司 | Method for purifying biological sulfur |
| CN111099784A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Treatment method of desulfurization wastewater |
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|---|---|---|---|---|
| CN102451607A (en) * | 2010-10-21 | 2012-05-16 | 李红玉 | Internal and external dual-circulation reaction method and device for absorbing hydrogen sulfide |
| CN102180549A (en) * | 2011-03-29 | 2011-09-14 | 重庆大学 | Method and system for zero emission treatment of desulfured waste water |
| CN102180549B (en) * | 2011-03-29 | 2013-07-17 | 重庆大学 | Method and system for zero emission treatment of desulfured waste water |
| CN103145244A (en) * | 2013-03-01 | 2013-06-12 | 中国石油化工股份有限公司 | Synergistic biological treatment method for washing waste water and amine salt waste liquor produced by capturing CO2 in smoke of coal-fired power plant |
| CN104998529A (en) * | 2015-02-12 | 2015-10-28 | 太仓意发石化矿材检测有限公司 | Method for utilizing boiler waste gas in fermentation alcohol production |
| CN104801166A (en) * | 2015-04-22 | 2015-07-29 | 华南师范大学 | Method and device for cooperative flue gas desulfurization and sewage organic matter degradation and denitrification |
| CN107961653A (en) * | 2017-11-22 | 2018-04-27 | 中冶京诚工程技术有限公司 | A kind of dual alkali scrubbing FGD process modified technique and system |
| CN111099784A (en) * | 2018-10-26 | 2020-05-05 | 中国石油化工股份有限公司 | Treatment method of desulfurization wastewater |
| CN110550608A (en) * | 2019-09-18 | 2019-12-10 | 中国石油化工股份有限公司 | Method for purifying biological sulfur |
| CN112429832A (en) * | 2020-12-11 | 2021-03-02 | 江苏宏梓新能源科技有限公司 | Sodium borohydride tail gas absorption liquid recycling device and method |
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